Process of making aldehydes and solutions thereof.



No. 868,320. v PATENTED 001. 15, 1907.

H. s. BLAGKMORE.

PROCESS OFMAKING ALDEHYDES' AND SOLUTIONS THEREOF.

APPLICATION FILED APR. 20, 1903.

r I I I I F 4 A r r w\" \\assa% \Wl awn a; W yon/M UNITED STATES PATENTOFFICE. HiENRY SPENCER BLACKMORE, OF MoUnT VERNON, NEW Yo-Rx.

PROCESS or MAKING ALnEnYnns Ann somrrrons manor.

No. 868,320. Specification of Letters Patent. Patented Oct. 15, 190.7.Application filed April 20, 1903. Serial No. 153,424- v V To all whomitmay concern: In carrying out my invention for the production of Be itknown that I, HENRY SPENCER BLACKMORE, a formic aldehyde I proceed asfollows,.reference being citizen of the United States, residing at MountVernon, had to the accompanying drawing which illustrates a in thecounty of Westchester and State of New York, preferred form of apparatuswhich I employ for the have invented certain new and useful Improvementsin purpose. p 60 Processes of Making Aldehydes and Solutions Thereof;Referring to the drawing, Figure 1 is a yertical lonand I do herebydeclare the following to be' a full, clear, gitudinal section of myapparatus, Fig; 2 is an enand exact description of the invention, suchas will enlarged vertical section showing the electric diaphragms ableothers skilled in the art to which it appertains to and the connectionsof the transforming chamber, and

make and use the same. Fig. 3 is a cross section of one ofthe rings andelectric 65 The object of my invention is to produce aldehydesconnection of the transforming chamber andan elec-' i and solutionsthereof and consists in oxidizing hydrotric gauze diaphragm connectedtherewith. carbon or substitution products thereof in the presence ISimilar letters refer to corresponding parts in the of a fluid capableof absorbing, occ'luding, or combining several views.

with the aldehyde produced in such a manner as not to The letter Adesignates a transforming chamber of 70 injure its natural propertieswhile maintaining the cylindrical or other form, provided at its topwith an transforming ingredients at a temperature below that elbow B andpipe 0, the latter connected with'a jackat which aldehyde isdissociated, by the abstraction eted condenserD in any desired,air-tight manner. or neutralization of heat liberated during transforma-The lower end. of the transforming chamber A is pro-v tion byrefrigeration or other convenient means and vided with a detachable headE, having a cential stuff- '75 producing solutions of the aldehyde bythe final coning box or screw-threaded plug F of insulating materialdensation of the ingredients. connected therewith and in which is fitteda rod or elec- My invention relates specifically to the production tricconnection G, the upper portion of which is formed of formic aldehydefrom methyl nydroxid (wood alcoin sections having screw threadedconnections, as

2-5 hol) by the action of oxidizing agents, such as free oxyshown at a,a, a, in Fig. 2. 80 gen or oxygen-yielding compositions, while in commu-The transforming chamber A, like the electric connication with a fluidcapable of absorbing, occluding, nection G, is partly composed ofsections as shown at or combining with the formic aldehyde thus producedI), b, b, see Figs. 1 and 2, the said sections being and at the sametime neutralizing the heat liberated joined together by the threadedends 0, o, c.

during the oxidation by absorption, such as steam; the A series ofmetallic gauze diaphragms d are arranged 8.5 oxidation of the methylhydroxid maybe induced by within the transforming chamber A, the saiddiaphragms primarily heating to the point of reaction, either with beingsecurely held in relative positions by the abutting direct heat orthrough the medium of electrical resistshoulders of the screw-threaded"endsfof the transformance, either or both of which may ormay not beaug- 'ing chamber rings and of the central connection thereof.

mented by the presence of so-called catalytic sub The upper and lowerdiaphragms d and d are ar- '90 stances, such as platinized asbestos.ranged in several thickness, forming a heat absorber In the formation ofsolutions of aldehydes, especially and flash preventer, and insulatedfrom the electric formic aldehyde, which is a gas, in water orothersolconnection G as shown at e, e, for thepurposes hereinventagents, great difficulty has been found to produce after fullydescribed. 3 i

40 solutions which will remain permanent inasmuch as Peep holes f, f,having mica fronts or covers hfli, 95 there appears to be a tendency topolymerize into paraare located at the opposite sides of the combustionor formaldehyde or trioxymethylene and intermediate transformingcompartments A to enable the attendant polymerization products, whichpolymers are only to view the interior thereof, and provide forregulatin with difficulty rendered utilizable for disinfectant or theapparatus as occasion may require.

germicide agents. The letters'i and i" and a designate electric wires100 My invention also has for another object the producwhich are,respectively, connected with the electric tion ofsolutions of formicaldehyde and other aldehydes conductor G and the walls of thetransforming chamber .of permanent character with reference tospontaneous A by ordinary means.

dissociation, decomposition,. or polymerization, by The lower part ofthe transforming chamber is progenerating the aldehyde in the presenceof a solvent vided, horizontally, with a pipe-section H having a .105fluid, whereby, in its nascent condition, it appears to detachable endor head h within which is tightly fit-Y have the propertyofbeiugabsorbed, occluded, or unitcd ted a tube Z, the latter providedwith a '1 head Z and I with the solvent vehicle in a more permanentmanner an inlet pipe or; while within the stem of the! head andproducing solutions from which the difficulty of and the tube Z isarranged a pipe n for the purposes here polymerization appears to beeradicated. inafter fully specified. p

In the operation of my invention for the production of formic aldehyde 1take methyl hydroxid (wood alcohol) and vaporize it by means of heatcommunicated thcrcto through a steam coil or by the action of live steamor a current of heated gas, and convey it into the transformingapparatus described, through the pipe n. I then introduce oxygen or airthrough the pipe m regulating it in about equivalent proportions totransform the methyl hydroxid into formic aldehyde as hereinafter setforth. I also introduce into the apparatus, together with the methylhydroxidi and oxidizing agent,

va fluid capable of absorbing, occluding, or combining with the formicaldehyde generated to produce liquid compositions; which fluid does notinjure or deteriorate the disiniectant'or germicide properties of formicaldehyde and which fluid is capable of absorbing, to a large extent, theheat generated by the oxidation of the methyl. alcohol, in generatingthe formic aldehyde, and thereby maintaining the temperature below thepoint at which formic aldehyde is dissociated by the action of heat.This fluid, such as steam, which I prefor to employ in making aqueoussolutions, may be in- I come thoroughly mixed in the lower part of thechamber A together with the absorbing or occluding fluid, such as steam.and then pass up through the insulated gauze flash preventerid into thetransforming compartment A. i

A current of electricity is then passed through the con nections i, i,i, the same passing through the diaphragms (ld heatingthem in proportionto the strength of the current to a low red heat, the said current beingregulated to maintain the temperature at this point i with reference tothe volume of fluids passing through the gauze and excess of heat whichmay beliberated during oxidation or transformation, the temperaturebeing somewhat gaged by the color of the diaphragm which can be observedthrough the mica-closed peepholes f, f or by means of thermometerssuitably communicating with the innerchamber of the apparatus (notshown), as desired; as the mixture of methyl hydroxid vapor, oxygen oroxygen-yielding composition and heat absorbing fluid capable of unitingwith once:

cluding the formic aldehyde formed, comes in contact with the heatedgauze diaphragms, the oxidation of the methyl hydroxid is induced,forming formic aldehyde,

which becomes thoroughly absorbed by thesurrounding absorbent fluid, andyielding heat, which heat is prevented from becoming sensible to anyconsiderable "degree, by the heat-absorbing properties ofthe surroundingfluid The reaction which takes place maybe illustrated by the followingchemical formula or equa-' I Whenthe-hydrocarbon,methane (methyl hydrid,

OH3-H) is employed to. formic aldehyde instead of the methane hydroxylsubstitution produibt,

methyl hydroxid, (wood alcohol CH OH), the reaction which takes placemay be illustrated by the following formula or equation:

diaphragms to a bright red, which temperature is re duced by the firstportions of fluids coming in contact therewith, to a low red. As soon asthe oxidation of the methyl alcohol or methane commences, however, the

heat liberated thereby naturally has a tendency to increase thetemperature of the diaphragm at which time the electricity supplied tothe diaphragm is gradually cut off so that the temperature of thediaphragnis may be maintained at a low red by thecombined action of theheat liberated during the formation of the aldehyde and the resistanceof the reduced electrical current. It should be noted in the performanceof this process that the formation of aldehyde by oxidation occurs inthe sphere in juxtaposition to the heated diaphragms located within andsurrounded by a body of heat-absorbing fluid and the temperature of thedia-- phra'gms is therefore not indicative of; the temperature of thebody offluid as a whole.

The current of vapor and gas introduced passing rapidly from theapparatus arrics the product of rcaction quickly through and away fromthe heated.

gauze diaphragms and from the flash. prcvcntcr I! which consists of anumber of layers of garlic, insulatcd employing steam as absorbing agcnlI' can usc-aqucous moisture orothcr fluid introduccd in any convcnientmanner so long as thefabsorbing fluid is present. during the formationof the aldehyde.

It will be observed that the transforming compartmcnt A in whichthe'clcctrically 'hcatcd diaphragms arc located is protected at theinner and outcr portions with heavy insulated gauze scctions whichprevents the igniting mixture of gases, in said compartment. fromcarrying the flash outside. of thc com 'iartincnt and admits of'controlling the temperature and the product by rapidity-of admission ofgases thereto during transformation, the electric diaphragms d-d beingmaintaincd at uniform temperature.

I can produce other aldehydcsby employing other ,alk'yl hydroxids or bythe oxidation of other alkyl compounds or. substitution products ofhydrocarbon, the neutralizing element or substituted elements ordiaphragms of so-called catalytic or contact substances radicals ofwhich are capable of being displaced by oxygen, without departing fromthe spirit of my invention which consists in oxidizing hydrocarbons ortheir substitution products, such as alkyl hydroxids,

by the action of oxygen or oxygen-yielding substances while in thepresence of a fluid capable of absorbing,

occluding, or combining with the aldehyde produced without injuring itsproperties and also capable of ab.-

sorbing the heat liberated during oxidation of the alkyl.

droxid and oxygen as it crimes in contact therewith and the excess ofheat either absorbed therefrom or liberated by reaction is absorbed bythe surrounding introduced, the heat generated being abstractedsorapidly that the temperature is maintained below the point at whichthe aldehyde is dissociated by the action oi heat.

Instead of simply employing the heating diaphragms d-d as a means forinducing oxidation I can augment the oxidizing process by the placingbetween the said (not shown), if I so desire.

I have found by generating formic aldehyde by the oxidation of methylhydroxid in thepresence oisteam and condensing the steamcarrying theformic aldehyde thus generated, that the formic aldehyde seems to beoccluded, retained or dissolved in the condensed steam in a morepermanent manner than can be produced by other means.

Instead of steam I can also use other fluids, such as vaporized camphoroil, in which case solutions of formic aldehyde in the oil or otherfluid employed, are obtained. In the case of employment of camphor oil,however, care should be taken to employ the same in such excess and toregulate the temperature of the reacting ingredients by reirigeration insuch a manner, that the camphor oil does not become oxidized to theexclusion of the methyl hydroxid.

I can produce aldehyde in accordance with the proc-.

ess as herein set forth either under reduced or increased pressure or,in some cases, the reacting or absorbing in-v clude hydrocarbons per se;such as methyl hydrid,

(methane), as well as other alkyl compounds produced by the substitutionof otherelements or radicals for the hydrogen of the hydrocarbon, suchas hydroxyl, (OH), as iound in alcohols, which substituted elements orradicals are capable of being displaced together with other hydrogens ofthe compound by oxygen, with the formation of aldehyde; andthe termgaseous,

as applied to fluids throughout this specification and claims, isintended to include vaporized bodies or substances as well as gases perse which are capable, after treatment, oLbeing condensed in liquid form,and the relation of the absorbing fluid'to the aldehyde, refers tofluids capable of absorbing, occluding, dissolving, or uniting with thealdehyde formed without detoriorating or affecting the naturalproperties of the aldehyde or which are inert to it thereby producingsolutions thereof when recovered in liquid form.

Having now described my invention, what- I claim as new and desire tosecure by Letters Patent is:-

term fassociation employed with reference to the '1. The process ofmaking aldehydes which consists in oxidizing alkyl compounds in thepresence of an aldehydeabsorbing fluid while maintaining the temperaturebelow the dlssociating'polnt of the aldehyde desired by abstract lug theheat liberated during oxidation.

2. The process of making aldehydes which consists in oxidizingsubstitution products of hydrocarbon in the presenceof analdehydeabsorbing fluid .while maintaining the temperature below thedissociating point of the aldehyde desired by abstracting the heatliberated during oxidation.

3. The process of making aldehydes which consists in oxidizing hydroxylsubstitution products of hydrocarbon in the presence of analdehyde-absorbing fluid while main-' taining the temperature below thedissociating point of the aldehyde desired by abstracting the heatliberated during oxidation.

4. The process of making formic aldehyde which consists in oxidizingmethyl alcohol in the presence of an aldehyde-absorbing fluid whilemaintaining the temperature below the dissociating point of the aldehydedesired by abstracting the heat liberated during oxidation.

5. The process of making formic aldehyde which con sists in oxidizingmethyl alcohol in the presence of an aldehyde-absorbing fluid whilemaintaining the temperature below the dissociating point of formicaldehyde by refrigeration.

6. The process of making formic aldehyde which con sists in oxidizingvaporized methyl hydroxid in the presence of an aldehyde-absorbing fluidand abstracting the heat liberated, by refrigeration, therebymaintaining the temperature below the' dissociating point of thealdehyde desired.

7. The process of making formic aldehyde which con sists in exposing thevapor of methyl hydroxid to the action of oxygen in the presence of analdehyde-absorbing fluid at a reacting temperature and maintaining thetemperature below the decomposing point of formic aldehyde byabstracting the heat liberated by the said reaction.

S. The process of making aldehyde solutions which con sists in oxidizingalkyl compounds in the presence of a fluid capable of association withthe aldehyde produced while maintaining the temperature below thedissociating point of the aldehyde desired by abstracting the heatliberated during oxidation and'finally recovering the'aldehyde solutionin liquid form by condensation.

9. The process of making aldehyde solution which cons'ists in oxidizingalkyl compounds in the presence of a gaseous body capable of associationwith the aldehyde produced while maintaining the temperature below thedis.- sociating point of the aldehyde desired by abstracting the heatliberated during oxidation and finally recovering the aldehyde solutionby condensing the said gaseous body together with the formic aldehyde.

10. The process of making aldehyde solutions which consists in'oxidizlngalkyl hydroxlds in the presence of a fluid capable of associatlon withthe formic aldehyde 11. The process of making aldehyde which consists inoxidizing an alcohol in the presence of an aldehyde-absorbingfluid-capable of association with the aldehyde produced, and maintainingthe temperature of the transforming ingredients below the point at whichthe aldehyde is dissociated by the action of heat, by the refrigerativeaction of heat-absorbing fluid.

12. The processof making formic aldehyde which consists in oxidizingmethyl alcohol in the presence of a solvent fluid capable of associatingwith formic aldehyde while maintaining the temperaturebelow the point atwhich formic aldehyde is dissociated by the action of heating the heatliberated thereby by refrigeration, thereby maintaining the temperaturebelow the dissociating point ot'said formic aldehyde.

. of'a formic aldehydeabsorbing fluid and maintaining the.

15. The process of making formic aldehyde which con- .sists in exposingthe vapor of methyl hydroxid to the action of oxygen at a reactingtemperature in the presence temperature below the dissociating point offormic aldehyde by abstracting the heat liberated during oxidation.

16. The process of making formic aldehyde which consists in oxidizingmethyl hydroxid in the presence of steam and maintaining the temperaturebelow the dissociating point of formic aldehyde by abstracting the heatliberated by the said reaction. I

17. .The process of .making formic aldehyde which corisists in oxidizingmethyl hydroxid in the presence of steam while maintaining thetemperature below the dissociating point of formic aldehyde by theabstraction of heat and solution of formic aldehyde, substantially asdescribed.

19. The process ofmaking aldehydes which consists in establishing asphere of reaction between alkyl compounds and oxidizing agents within abody of heat-absorbing aide hydesolvent fluid and maintaining thereaction therein by supplying reactingingredients thereto whilemaintaining the temperature within the said sphere at a reactingpointand below the temperature at which the aldehyde dissociates by theaction of heat.

In testimony whereof I affix my signature, in presence of two witnesses.

i HENRY SPENCER BLACKMORE. Witnesses 2 C. C. Wmcirr,

H. N. JENKINS.

